Porous ceramic material and producing method of same, and valve unit

ABSTRACT

A porous ceramic material for a slidable member or unit such as a valve unit of a combination faucet. The porous ceramic material comprises a ceramic sintered body which is formed with pores dispersedly located therein. The pores are defined respectively by surface layers forming part of the ceramic sintered body. Each surface layer contains silicon in a content higher than that in other part of the ceramic sintered body. The porous ceramic material is prepared, for example, first by mixing ceramic powder and hollow particles each of which contains silicon so as to obtain a mixture; then by forming the mixture into a predetermined shape to obtain a formed body; and finally by sintering the formed body at a temperature higher than a melting point of each hollow particle to thus obtain the sintered body formed with pores and containing silicon.

This application is a division of application Ser. No. 08/557,840, filedNov. 14, 1995, now U.S. Pat. No. 5,688,728.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to improvements in a porous ceramic material anda method of producing the porous ceramic material, and a valve unitincluding a slidable member formed of the porous ceramic material, inwhich the porous ceramic material is high in durability under thermalshock and thermal stress while maintaining a high slidingcharacteristics even upon a long time use.

2. Description of the Prior Art

Hitherto a variety of methods have been proposed and put into practicaluse in order to improve a sliding characteristics of a slidable member,for example, of a valve of a combination faucet (for hot water and coolwater) or of a mechanical seal ring. One of the methods is to form theslidable member of a material which is prepared by impregnating a porousceramic material having a three-dimensional network structure, withlubricating oil. Another one is to select the smoothness of the slidingsurface of a slidable member formed of a porous ceramic material, tofall below a predetermined value as disclosed in Japanese PatentProvisional Publication No. 6-58434. A further one is to select thesurface roughness of the sliding surface of a slidable member formed ofa porous ceramic material, to fall within a predetermined range asdisclosed in Japanese Patent Provisional Publication No. 6-32646.According to the above methods, the sliding characteristics of theslidable member can be improved under the action of the lubricating oilto be exuded to a sliding surface, or under the action of pores locatedat and open to the sliding surface. In general, such a porous ceramicmaterial is produced as follows: First, resin particles formed of asynthetic resin such as epoxy resin, phenolic resin or acrylic resin aremixed in ceramic powder to prepare a mixture. The mixture is then formedinto a predetermined shape by using a metallic mold cress or the likethereby to form a formed body in which resin particles are dispersed.Finally, the formed body is sintered to form the porous ceramicmaterial. During this sintering, the resin particles in the formed bodyis burnt or decomposed to be extinguished so that pores are formed inthe ceramic material.

However, such a porous ceramic material has a tendency to be not alwayshigh in thermal shock resistance as compared with a ceramic materialformed with no pores even though it is improved in slidingcharacteristics.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an improved porousceramic material which can overcome drawbacks encountered inconventional porous ceramic materials.

Another object of the present invention is to provide an improved porousceramic material which is suitable to be used as a slidable member orthe like and is high in thermal shock resistance as compared with theconventional porous ceramic materials.

A further object of the present invention is to provide an improvedporous ceramic material producing method which makes possible to form aporous ceramic material which is thermal shock resistance, withoutraising a production cost and without using troublesome operations.

A still further object of the present invention is to provide animproved valve unit formed of a porous ceramic material which is high indurability under thermal shock and thermal stress while maintaining agood sliding characteristics even upon a long time use.

A first aspect of the present invention resides in a porous ceramicmaterial comprising: a ceramic sintered body which is formed with poresdispersedly located in the sintered body, the pores being definedrespectively by surface layers forming part of the ceramic sinteredbody; and silicon contained in the ceramic sintered body, a content ofsilicon being higher in at least a part of the surface layers than thatin other part of the ceramic sintered body.

According to this aspect, the porous ceramic material is not onlyexcellent in sliding characteristics but also sufficiently high inthermal shock resistance.

A second aspect of the present invention resides in a method ofproducing a porous ceramic material, comprising the following steps inthe sequence set forth: (a) mixing ceramic powder and hollow particleseach of which contains silicon so as to obtain a mixture; (b) formingthe mixture into a predetermined shape to obtain a formed body; and (c)sintering the formed body at a temperature higher than a melting pointof each hollow particle to obtain a sintered body formed with pores andcontaining silicon.

A third aspect of the present invention resides in a porous ceramicmaterial comprising: a ceramic sintered body which is formed with poresdispersedly located in the sintered body, the pores being definedrespectively by surface layers forming part of the ceramic sinteredbody; and silicon contained in the ceramic sintered body, a content ofsilicon being higher in at least a part of the surface layers than thatin other part of the ceramic sintered body. The porous ceramic materialis produced by a method including the following steps in the sequenceset forth: (a) mixing ceramic powder and hollow particles each of whichcontains silicon so as to obtain a mixture; (b) forming the mixture intoa predetermined shape to obtain a formed body; and (c) sintering theformed body at a temperature higher than a melting point of each hollowparticle to obtain the ceramic sintered body formed with pores andcontaining silicon.

A fourth aspect of the present invention resides in a slidable memberformed of a porous ceramic material including a ceramic sintered bodywhich is formed with pores dispersedly located in the sintered body, thepores being defined respectively by surface layers forming part of theceramic sintered body, and silicon contained in the ceramic sinteredbody, a content of silicon being higher in at least a part of thesurface layers than that in other part of the ceramic sintered body. Theslidable member comprises a main body, and means defining a slidingsurface at a part of the main body, the sliding surface being inslidable contact with a member independent from the main body.

A fifth aspect of the present invention resides in a valve unitcomprising: a liquid supply-side member including at least one liquidsupply means through which liquid is supplied into the valve unit, andhaving a first sliding surface; a flow amount control member having asecond sliding surface which is in slidable contact with the firstsliding surface of the supply-side member, the flow amount controlmember being relatively rotatable to the liquid supply-side member so asto control an amount of the liquid to be supplied from the supply-sidemember; and liquid discharge means through which the liquid controlledin the amount is discharged from the valve unit, the liquid dischargemeans being formed at least one of the supply-side member and the flowamount control member. Each of the supply-side member and the flowamount control member is formed of a porous ceramic material including aceramic sintered body which is formed with pores dispersedly located inthe sintered body, the pores being defined respectively by surfacelayers forming part of the ceramic sintered body, and silicon containedin the ceramic sintered body, a content of silicon being higher in atleast a part of the surface layers than that in other part of theceramic sintered body.

According to the fifth aspect, component parts of the valve unit areformed of the porous ceramic material of the present invention andtherefore they are sufficiently high in durability under thermal shockand thermal stress while maintaining a good sliding characteristicstherebetween even upon a long time use.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of a sliding characteristics testingmachine used for testing of test pieces of a variety of samplesincluding one according to the present invention;

FIG. 2 is a scanning electron microscope (SEM) photograph of a surfaceof the test piece of a first sample (ceramic material) according to thepresent invention;

FIG. 3 is an enlarged SEM photograph of a part of the surface of thetest piece of the first sample;

FIG. 4 is an enlarged SEM photograph of a part of the surface of thetest piece of the second sample (ceramic material) according to thepresent invention;

FIG. 5A is a graph showing a spectrum of an energy dispersive X-rayanalysis of a part other than pores in the test piece of the secondsample;

FIG. 5B is a graph showing a spectrum of the energy dispersive X-rayanalysis of an inner surface portion of one of the pores in the testpiece of the second sample;

FIG. 6 is an enlarged SEM photograph of a part of the surface of thetest piece of the fifth sample;

FIG. 7A is a graph showing a spectrum of an energy dispersive X-rayanalysis of a part other than pores in the test piece of the fifthsample;

FIG. 7B is a graph showing a spectrum of the energy dispersive X-rayanalysis of the inner surface portion of one of the pores in the testpiece of the fifth sample;

FIG. 8 is an exploded perspective view of an essential part of a valveunit as an embodiment of a slidable member of the present invention;

FIG. 9 is a perspective view of a flow amount control member formingpart of the valve unit of FIG. 8, showing the back side of the controlmember; and

FIG. 10 is a perspective view of the essential part of the valve unit ofFIG. 8, in an assembled state.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, the porous ceramic materialcomprising: a ceramic sintered body which is formed with poresdispersedly located in the sintered body, the pores being definedrespectively by surface layers forming part of the ceramic sinteredbody; and silicon contained in the ceramic sintered body, a content ofsilicon being higher in at least a part of the surface layers than thatin other part of the ceramic sintered body. The porous ceramic materialis produced, for example, by a producing method comprising the followingsteps in the sequence set forth: (a) mixing ceramic powder and hollowparticles each of which contains silicon so as to obtain a mixture; (b)forming the mixture into a predetermined shape to obtain a formed body;and (c) sintering the formed body at a temperature higher than a meltingpoint of each hollow particle to obtain the ceramic sintered body formedwith pores and containing silicon.

The porous ceramic material of the present invention comprises theceramic sintered body. A main raw material (ceramic powder) of theceramic sintered body is, for example, Al₂ O₃ system powder, Si₃ N₄system powder, SiC system powder, AlN system powder, ZrO₂ powder and/orthe like. Accordingly, the sintered body obtained by the aboveproduction method has component particles which are generally the samein composition and crystal structure as the above powder of the main rawmaterial. The ceramic sintered body has many pores which are dispersedlylocated therein, in which each pore is defined by the surface of asurface layer forming part of a solid section of the sintered body. Eachof almost all the pores is surrounded with the surface layer so that thesurface of the surface layer defines a pore. The pores may be continuousto each other to form a long hole in the ceramic sintered body. Thesurface layer is higher in Si (silicon) content than other part of thesolid section of the sintered body. By virtue of this feature, theporous ceramic material of the ceramic sintered body becomesparticularly suitable for a slidable member having a sliding surfacewhich is in slidable contact with another member. It will be understoodthat a surface portion having the above sliding surface is formed withthe pores, in which some pores open to the sliding surface. Accordingly,for example, in case that a lubricant such as a lubricating oil issupplied to the sliding surface, the lubricant is retained in the openpores and exudes little by little, and therefore it is possible tomaintain a lubricating effect for a long time while improving a slidingcharacteristics of the slidable member. Even if in case that thelubricant is not supplied, an adhesion or linking phenomena causedbetween the slidably contacting surfaces when the smoothness of thecontacting surfaces is very high can be suppressed owing to existence ofthe open pores at the sliding surface thus similarly improving thesliding characteristics of the slidable member. Additionally, the layerhigh in Si content is formed surrounding each pore, and therefore theresultant porous ceramic material is high in thermal shock resistancesimilarly to a ceramic material which is not formed with pores.

An average size or diameter of each pore formed in the ceramic sinteredbody is larger than that of the main component particles (or the rawmaterial ceramic powder) of the ceramic sintered body in order that theporous ceramic material has a suitable retaining ability for thelubricant and a suitable linking suppressing effect while securelyobtaining a sealing ability between the contacting surfaces and asufficient strength of the ceramic sintered body itself. The averagesize of each pore in the ceramic sintered body is preferably within arange of from 5 to 300 μm, more preferably within a range of from 20 to250 μm, and further more preferably within a range of from 50 to 200 μm.A total volume of the pores formed in the ceramic sintered body ispreferably within a range of from 2 to 40% relative to the volume of theceramic sintered body, more preferably within a range 2 to 20%, andfurther more preferably within a range of from 3 to 10%.

The pores formed in the ceramic sintered body depend on the hollowparticles which are mixed with the raw material ceramic powder andcontained in the ceramic sintered body. In this regards, in case that anaverage particle size or diameter of each of the hollow particles is setwithin the range of from 20 to 250 μm, the average particle size of theraw material ceramic powder is set preferably within a range of from 1to 20 μm, more preferably within a range of from 2 to 5 μm, so that theaverage particle size of the pores formed in the ceramic sintered bodybecomes larger than that of the component particles of the ceramicsintered body.

During sintering of the formed body including the raw material ceramicpowder and the hollow particles, some hollow particles may crush andother hollow particles may maintain their inside space which forms eachpore in the ceramic sintered body after completion of the sintering.Each hollow particle is formed of a raw material containing Si(silicon). The raw material of the hollow particles is preferably onewhich has a melting point lower than a sintering temperature of the rawmaterial ceramic powder, or one which may react with a component of theraw material ceramic powder to form an eutectic crystal or the likewhich is relatively low in melting point. By using such a raw materialfor the hollow particles, the surface layer high in Si content can berelatively easily formed around each pore in the ceramic sintered body,i.e., formed at a portion near the surface in contact with the pores. Amechanism for forming such a high Si content layer seems to be that apart of a component of the hollow particle molten during the sinteringagain precipitates at the surface layer surrounding each pore. It issupposed that the thus precipitated substance at the surface layer fillsa gap or the like among particles of the raw material ceramic powder,exposed to the pore. This reinforces a portion which serves as astarting point of breakage of the ceramic sintered body, therebyimproving the thermal shock resistance of the porous ceramic material.Another part of the hollow particle component molten during thesintering flows into among the ceramic powders and serves as a kind ofsintering assistant, thereby providing an advantage of decreasing theadding amount of sintering assistants to the raw material ceramicpowder. The surface layer high in Si content may be formed in acrystalline state or in an amorphous (glass) state.

Each hollow particle is, for example, formed of a material of SiO₂system (containing SiO₂ as a main component), SiO₂ --Al₂ O₃ system(containing SiO₂ and Al₂ O₃ as main components), or the like. Thematerial of the hollow particle is suitably selected according to theraw material ceramic powder. Either of the materials of the SiO₂ systemand the SiO₂ --Al₂ O₃ system is compatible with the raw material ceramicpowder of the Al₂ O₃, and forms a low melting point reaction productupon reaction with the raw material ceramic powder. A particle size(diameter) of the raw material ceramic powder to be used and a mixingamount (ratio) relative to the amount of the raw material ceramic powderto be used are set in accordance with the average size and the volumepercentage of the pores in the ceramic sintered body. The shape of thehollow particles is preferably generally spherical because of providinggenerally spherical pores which can prevent formation of a portionserving as the starting point of breakage of the ceramic sintered body.In this case, the generally spherical shape means a spherical shape anda shape similar to the spherical shape (for example, a generally anegg-shape, and the shape of ellipsoid of revolution). It will beunderstood that each hollow particle is not necessarily generallyspherical and therefore may be of a shape which does not cause a portionserving as the starting point of breakage of the ceramic sintered body.An example of the spherical hollow particles of the SiO₂ --Al₂ O₃ isreadily available on the market under the trade name of "SHO BALLOON" ofShowa Denko Co., Ltd. Another example of the spherical hollow particlesis available under the trade name of "Micro Balloon" of Pacific ChemicalMarketing Company.

In case of using the hollow particles (for example, of the SiO₂ --Al₂ O₃system) containing two or more basic components, the hollow particlesmay be prepared by previously melting and mixing the basic components,or otherwise may be prepared by mixing separate basic components. Insuch a case, a composition (mixing) ratio between the basic componentsof the hollow particles are suitably selected so that the hollowparticles have a suitable melting temperature. In this regard, in casethat the hollow particles to be used is of the Al₂ O₃ --Al₂ O₃ system,the mixing ratio between SiO₂ and Al₂ O₃ is preferably such that thecontent of SiO₂ relative to total of SiO₂ and Al₂ O₃ is within a rangeof from 50 to 70% by weight.

In this case, it is preferable that the above porous ceramic materialhas a thermal shock resistance temperature which is not lower than 80%of that of a ceramic material which is formed with no pore. Here, meantby the term "ceramic material which is formed with no pore" is amaterial which is prepared by sintering a formed body obtained by a rawmaterial ceramic powder without addition of a pore-forming medium suchas the hollow particles. The thermal shock resistance temperature isrepresented by the following equation:

    ΔT=T-T0

where ΔT is the thermal shock resistance temperature; and T is thehighest value of a heating temperature at which value no crack isproduced in a test piece (having a predetermined shape and dimensions)of the ceramic material even under a thermal shock test which isconducted by locating the test piece upon heating into water having apredetermined temperature T0.

Next, the producing method of the porous ceramic material will bediscussed in detail. The producing method comprises the following steps:

(a) A mixing step: The ceramic powder and the hollow particles eachcontaining Si are mixed with each other to obtain a mixture;

(b) A forming step: The above mixture at the mixing step is formed intoa predetermined shape to obtain a formed body; and

(c) A sintering step: The formed body at the forming step is sintered ata temperature higher than a melting point of each hollow particle toobtain the ceramic sintered body formed with pores and containing Si.

In the mixing step, mixing of the raw material ceramic powder and thehollow particles is accomplished by using a known mixing or agitatingmachine such as a mixer in a dry method (without using liquid). However,such mixing may be accomplished in a wet method in which the rawmaterial ceramic powder and the hollow particles are mixed together withwater, solvent or the like to form a slurry.

In the forming step, the formed body is fabricated by a known mannersuch as a pressing using a metallic mold, an injection molding, a slipcasting, or the like. Here, in case of using the metallic mold pressing,it is preferable to add one of a variety of binders to the raw materialceramic powder in order to increase the strength of the formed body. Apressure during pressing in this case depends on kind and particledistribution and the like of the raw material ceramic powder and thehollow particles, in which the pressure is regulated within a range inwhich the resultant formed body has a suitable strength while preventingthe hollow particles from being crushed or damaged during fabrication orformation under the pressure. For example, in case that the hollowparticles of the SiO₂ --Al2O3 system are mixed with the raw materialceramic powder of the Al₂ O₃ system to prepare the material for theformed body, the pressing or fabrication pressure is set preferablywithin a range of from 0.5 to 2 t/cm². In case of using the injectionmolding, the raw material and the hollow particle are previously kneadedtogether with a resinous binder to prepare a compound; and then thecompound is injected from an injection machine into a metallic moldthereby obtaining a molded or formed body.

In case that the formed body contains inorganic binder(s) or organicbinder(s) such as resinous binder, it is preferable to add a binderremoving step before carrying out the sintering step, in order to removethe binder(s). In the binder removing step, the formed body is heatedfor a predetermined time at a temperature lower than a sinteringtemperature (the heating temperature in the sintering step) inatmospheric air, in a vacuum atmosphere or in other suitable atmospheresthereby evaporating, decomposing or burning the binder(s) or the like.In this binder removing step, a maintained heating temperature and aheating rate are suitably regulated in order to prevent the formed bodyfrom being damaged owing to abrupt occurrence of the evaporation,decomposition or the like of the binder(s) or the like.

In the sintering step, heating the formed body is carried out in avariety of atmospheres such as atmospheric air, a vacuum atmosphere, anitrogen gas atmosphere, a vacuum atmosphere containing oxygen. Kind ofthe atmosphere and the sintering temperature are suitably set inaccordance with kind of the raw material ceramic powder to be used,taking account of preventing the volume percentage of the pores formedin the sintered body from being excessively lowered upon contraction ofthe pores under the sintering having sufficiently proceeded. Forexample, in case of using the raw material ceramic powder of the Al2O3system, the sintering of the formed body is carried out in atmosphericair or in the vacuum atmosphere containing oxygen preferably at atemperature ranging from 1400° to 1700° C., more preferably at atemperature ranging from 1550° to 1650° C. A predetermined amount ofsintering assistant(s) may be added to the raw material ceramic powder.The sintering assistant(s) is SiO₂, MgO, CaO and/or the like in case ofusing the raw material ceramic powder of the Al₂ O₃ system. Under theeffect of the sintering assistant(s), mass transfer such as formation ofliquid phase and diffusion during the sintering is promoted thereby toincrease the density and therefore the strength of the sintered body. Asintering furnace used in the sintering step may be provided with apreliminary heating room in addition to a sintering room for thesintering, in which the binder removing step is carried out in thispreliminary heating room.

The thus obtained sintered body or porous ceramic material can be usedfor a variety of slidable members or units such as slidable componentparts, in a state as it is or upon being subjected to machining such ascutting and/or grinding.

An embodiment of such slidable members is a valve unit comprises (a) aliquid supply-side member including at least one liquid supply sectionthrough which liquid is supplied into the valve unit, and having a firstsliding surface; (b) a flow amount control member having a secondsliding surface which is in slidable contact with the first slidingsurface of the supply-side member, the flow amount control member beingrelatively rotatable to the liquid supply-side member so as to controlan amount of the liquid to be supplied from the supply-side member; and(c) a liquid discharge section through which the liquid controlled inthe amount is to be discharged from the valve unit, the liquid dischargesection being formed at least one of the supply-side member and the flowamount control member.

In the above valve unit, the at least one liquid supply section includesa high temperature liquid supply section through which a hightemperature liquid is supplied, and a low temperature liquid supplysection through which a low temperature liquid is supplied, the lowtemperature liquid being lower in temperature than the high temperatureliquid. Additionally, the flow amount control member has a mixingchamber in which the high and low temperature liquids are mixable witheach other, the mixing chamber being communicable with the high and lowtemperature liquid supply section and controllable relative to the highand low temperature liquid supply sections in accordance with a relativerotation of the flow amount control member to the supply-side member.

The above valve unit formed of the porous ceramic material of thepresent invention is usable, for example, for a faucet for hot water, ora combination faucet for hot water and cool water. Additionally, thevalve unit is excellent in sliding characteristics and high indurability under thermal shock and thermal stress due to contact betweenhot water and cool water thereby being prolonged in life.

EXPERIMENT

The following experiments are discussed merely to aid the understandingof the present invention, with reference to FIGS. 1 to 7B of thedrawings.

First, sintering assistant(s) containing SiO₂, MgO, CaO and the like wasadded to Al₂ O₃ powder having an average particle size of about 1 μm, inan amount of 10% by weight relative to the Al₂ O₃ powder. Apredetermined amount of binder was added to the mixture of the Al₂ O₃powder and the sintering assistant(s), and mixed in the wet methodthereby forming a binder-containing mixture. The binder-containingmixture was subjected to spray drying thereby obtaining granulated Al₂O₃ powder. To this granulated powder, 5% by volume of hollow particles(under the trade made of "SHO BALLOON" of Showa Denko Co., Ltd.) wasadded and mixed in a dry method. The hollow particles are generallyspherical and had an average particle size of 100 μm and of the SiO₂--Al₂ O₃ system. The mixture of the granulated powder and the hollowparticles was formed or fabricated at a pressure of 1.2 t/cm² by using ametallic mold press thereby to obtain the formed or molded body. Theformed body is fired or sintered at 1580° C. for 2 hours in atmosphericair thus obtaining a ring-shaped test piece having an outer diameter 30mm, an inner diameter of 10 mm and a thickness or height of 6 mm. Thistest piece was identified as that of a first sample (corresponding toExample 1)

Additionally, a test piece of a second sample (corresponding to Example2) having the same dimensions as those of the first sample was producedin the similar manner as that of the first sample with the exceptionthat the hollow particles of the SiO₂ system was used in place of thehollow particles of the SiO₂ --Al₂ O₃ system (the former hollowparticles had the generally same particle size as that of the latterhollow particles). Further, for the comparison purpose, test pieces ofthird, fourth, fifth and sixth samples (corresponding to ComparativeExamples 1, 2, 3 and 4, respectively) having the same shape anddimensions as those of the sample were produced in the similar manner asthat of the first sample except for the followings: In production of thetest piece of the third sample (Comparative Example 1), epoxy resinparticles having an average particle size of 100 μm were used in placeof the hollow particles; In production of the test piece of the fourthsample (Comparative Example 2), acrylic resin particles having anaverage particle size of 100 μm were used in place of the hollowparticles; In production of the test piece of the fifth sample(Comparative Example 3), phenolic resin particles having an averageparticle size of 100 μm was used in place of the hollow particles; andIn production of the test piece of the sixth sample (Comparative Example4), no hollow particle was added and therefore no pore was formed in thetest piece.

Two test pieces were prepared for each of the first to sixth samples.The prepared test pieces were subjected to a sliding characteristicstest to measure a sliding characteristics of each test piece by using asliding characteristics testing machine T as shown in FIG. 1. Thesliding characteristics test was conducted as set forth below. First,grease G was applied to an upper surface P1 of a lower-side test piece 1and to a lower surface P2 of an upper-side test piece 2. The lower-sideand upper-side test pieces 1, 2 were located one upon another in amanner that the grease-applied surfaces P1, P2 of them were in contactwith each other. The lower-side test piece 1 was fixed on a rotatabledrive shaft 3, while the upper-side test piece 2 was fixed to arotatable pressing shaft 4. Subsequently, a whole unit including thetest pieces 1, 2 and the shafts 3, 4 was dipped in pure water W having atemperature of 20° C., in which a load of 50 kgf was applied through thepressing shaft 4 so as to press the upper-side test piece 2 onto thelower-side test piece 1. Under this state, the lower-side test piece 1was driven or rotated at a rotational speed of 400 r.p.m. by therotating shaft 3. Here, when the sliding characteristics between theupper-side test piece 2 and the lower-side test piece 1 was lowered soas to initiate to rotate together as a one-piece, the torque applied tothe pressing shaft abruptly increased. This abruptly increased torquewas detected by a torque measuring device (not shown). Simultaneously,measurement was made on a time duration (sliding-durability time) t froma time point of starting of rotation of the rotating shaft 3 to a timepoint of detecting the above abruptly increased torque. The slidingcharacteristics of the test pieces of each sample was evaluated with thesliding-durability time t. Result of measurement of thesliding-durability time t (min.) is shown in Table 1.

Next, each test piece was heated and maintained at a predeterminedtemperature for 40 minutes, and immediately thereafter it was put intowater having a temperature of 20° C., upon which production of crack inthe test piece was confirmed under a visual observation. This operationwas repeatedly carried out upon changing the heating temperature (or theabove predetermined temperature), thereby measuring the highest value Tof the heating temperature at which crack cannot be produced.Accordingly, the thermal shock resistance temperature ΔT of each testpiece was obtained by subtracting the temperature T0 of the water fromthe heating temperature T. The rate (%) of the thermal shock resistancetemperature ΔT of each test piece of the first to fifth samples relativeto that of the test piece of the sixth sample (formed with no pore) wascalculated.

The results of measurements of the thermal shock resistance temperatureΔT and the rate (%) of ΔT of the first to fifth samples relative to thatof the sixth sample are shown in Table 1.

                                      TABLE 1    __________________________________________________________________________              Thermal shock                        Rate (%) of ΔT    Sample    resistance temp.                        relative to                               Sliding-durability    (Test piece)              ΔT (°C.)                        6th sample                               time t (min)    __________________________________________________________________________    1st Example            1 170       85     300    2nd     2 180       90     300    3rd     1 140       70     250    4th Comparative            2 130       65     300    example    5th     3 150       75     150    6th     4 200       --     100    __________________________________________________________________________

According to the test results in Table 1, the sliding-durability time tof each test piece of all the first to fifth samples (formed with thepores) is longer than that of the sixth sample (formed with no pore).Additionally, each test piece of the first and second samples (accordingto the present invention) exhibits a thermal shock resistancetemperature ΔT which is over 80% relative to that ΔT of the test pieceof the sixth sample (formed with no pore). In contrast, each test pieceof the third to fifth samples (the resin particles were used as thepore-forming medium) exhibits a thermal shock resistance temperature ΔTwhich is below 80% relative to that ΔT of the test piece of the sixthsample. Accordingly, it will be appreciated that the porous ceramicmaterial of the present invention is not only excellent in the slidingcharacteristics but also high in thermal shock resistance.

Thereafter, polishing was made for the surface of each test piece of thefirst and second samples (using the hollow particles of the SiO₂ --Al₂O₃ system and the SiO₂ system, respectively) according to the presentinvention and for the surface of the test piece of the fifth sample(using the phenolic resin particles) thereby exposing the polishedsurface of each test piece. The structure of the polished surface wasobserved by a scanning electron microscope (SEM). Additionally,regarding the test pieces of the second and fifth samples, a compositionanalysis for an inner surface portion of one of the pores and a partother than the pores was conducted by using an energy dispersive X-rayanalysis (EDS) provided to the scanning electron microscope. The term"inner surface portion" means a portion including a surface definingeach pore.

FIG. 2 is a SEM photograph (at 30 magnifications) of the surface of thetest piece of the first sample, in which it was observed that many pores(large dark spots in the photograph) are formed in the ceramic sinteredbody. FIG. 3 is an enlarged SEM photograph (at 1000 magnifications) of aportion around one of the pores. This photograph shows that columnarmatters are formed together with component particles of the ceramicsintered body. FIG. 4 is an enlarged SEM photograph (at 1000magnifications) of a portion around one of pores in the test piece ofthe second sample, and shows that a large amount of columnar matters areformed at the surface portion of the pore. FIGS. 5A and 5B show EDSspectrums of the part other than the pores and the surface of the innersurface portion of the pore, respectively. These figures depict that thepeak of Al is predominant so that the peak of Si is very low in theportion other than the pores, while a large peak of Si appears at theinner surface portion of the pore.

FIG. 6 is an enlarged SEM photograph (at 1000 magnifications) of aportion around one of pores of the test piece of the fifth sample, inwhich no formation of columnar matters is shown. FIGS. 7A and 7B showEDS spectrums of a part other than the pores and the inner surfaceportion of the pore, respectively. These figures depict that the peak ofSi is low both at the inner surface portion of the pore and in the partother than the pores.

It is supposed that the above columnar matters appeared at the innersurface portion of the pore constitute the surface layer (for each pore)high in Si content, as shown in FIGS. 3 and 4.

EMBODIMENT

Hereinafter, a concrete example of the above-mentioned embodiment of theslidable member or unit will be discussed with reference to FIGS. 8 to10.

Referring to FIGS. 8 to 10, a valve unit as an example of the slidablemember or unit is illustrated by a reference numeral 10. The valve unit10 is used, for example, as a valve section of a combination faucet formixing liquids (such as hot water and cool water) which are different intemperature. The valve unit 10 comprises a supply-side member 11, and aflow amount control member 12. Each member 11, 12 is formed generallydisc-shaped as shown, or may be otherwise formed plate-shaped. The flowamount control member 12 is formed at its lower face with a slidingsurface 13a. The supply-side member 11 is formed at its upper face witha sliding surface 13b. The flow amount control member 12 and thesupply-side member 11 are put one upon another in such a manner that thesliding surfaces 13a, 13b are in slidable contact with each other. Theflow amount control member 12 and the supply-side member 11 are bothformed of the porous ceramic material according to the presentinvention, and disposed within a casing (not shown) to which inflow andoutflow pipes and like are connected.

The supply-side member 11 is provided with high and low temperatureliquid supply sections 14, 15 which pierce the member 11 in a directionof thickness of the member 11. The high temperature liquid supplysection 14 includes a high temperature liquid inflow opening 14a whichis formed through the lower face of the supply-side member 11, and ahigh temperature liquid outflow opening 14b formed through the slidingsurface 13b of the supply-side member 11. Similarly, the low temperatureliquid supply section 15 includes a high temperature liquid inflowopening 15a which is formed through the lower face of the supply-sidemember 11, and a high temperature liquid outflow opening 15b formedthrough the sliding surface 13b of the supply-side member 11. Hightemperature liquid (such as hot water) is introduced from an inflow pipe(not shown) through the opening 14a to the opening 14b, while lowtemperature liquid (such as cool water) is introduced from anotherinflow pipe (not shown) through the opening 15a to the opening 15b. Theliquids from the liquid outflow openings 14b, 15b are flown into theflow amount control member 12. Additionally, the supply-side member 11is provided with a liquid discharge section 16 which pierces the member11 in a direction of thickness of the member 11. The liquid dischargesection 16 includes a liquid inflow opening 16b formed through thesliding surface 13b of the supply-side member 11, and a liquid outflowopening 16a formed through the lower face of the supply-side member 11.Accordingly, the liquid from the flow amount control member 12 is flownback to the side of the supply-side member 11 and introduced through theopening 16b to the opening 16a. The liquid from the opening 16a isdischarged through the outflow pipe connected to the casing.

The flow amount control member 12 is formed with a mixing chamber 17opened to the sliding surface 13a as also shown in FIG. 9. The mixingchamber 17 overlaps with and is in communication with the high and lowtemperature liquid supply sections 14, 15 and the liquid dischargesection 16, so that high temperature liquid from the high temperatureliquid supply section 14 and the low temperature liquid from the lowtemperature liquid supply section 15 are mixed and discharged throughthe liquid discharge section 16. Here, as shown in FIG. 10, the flowamount control member 12 is relatively rotatable to the supply-sidemember 11 so that a ratio between the high and low temperature liquids(respectively from the high and low temperature liquid supply sections14, 15) supplied to the mixing chamber 17 is changed in accordance withthe relative rotation between the flow amount control member 12 and thesupply-side member 11, i.e., in accordance with a ratio in area betweenthe low and high temperature liquid supply section 14, 15 overlappedwith the mixing chamber 17 of the flow amount control member 12.

In operation, as shown in FIG. 8, when the flow amount control valve 12is rotated to the side of the high temperature liquid supply section 14under the action of a lever 18 or the like, the overlapped area betweenthe liquid outflow opening 14b and the mixing chamber 17 increasesrelative to that between the liquid outflow opening 15b and the mixingchamber 17, increasing the ratio of the high temperature liquid flowinginto the mixing chamber 17 relative to the low temperature liquidflowing into the mixing chamber 17. As a result, the temperature of amixed liquid discharged through the liquid discharge section 16 rises.Conversely, when the flow amount control valve 12 is rotated to the sideof the low temperature supply section 15, the ratio of the lowtemperature liquid relative to the high temperature liquid increases,and therefore the temperature of the mixed liquid discharged through theliquid discharge section 16 lowers. Thus, by regulating the rotationalangle of the flow amount control member 12, the temperature of the mixedliquid to be discharged through the liquid discharge section 16 can befreely changed. The liquid discharge section 16 may be formed on theside of the flow amount control member 12.

The above supply-side member 11 and the flow amount control member 12 ofthe valve unit 10 are formed of the porous ceramic material of thepresent invention, and therefore they are sufficiently high indurability under thermal shock and thermal stress while maintaining agood sliding characteristics between the members 11, 12 even upon a longtime use.

While only the valve unit of the combination faucet has been shown anddescribed in detail as an embodiment formed of the porous ceramicmaterial of the present invention, it will be appreciated that theporous ceramic material of the present invention may be used not onlyfor other valves such as a valve adapted to simply stop and allow liquidflow or a valve adapted to control the flow amount of liquid, but alsofor a slidable member or unit other than valves, for example, amechanical seal or a slidable member to be used under the existence oflubricant.

What is claimed is:
 1. A valve unit comprising:a liquid supply-sidemember including at least one liquid supply section through which liquidis supplied into said valve unit, and having a first sliding surface; aflow amount control member having a second sliding surface which is inslidable contact with said first sliding surface of said supply-sidemember, said flow amount control member being relatively rotatable tosaid liquid supply-side member so as to control an amount of said liquidto be supplied from said supply-side member; and a liquid dischargesection through which said liquid controlled in the amount is dischargedfrom said valve unit, said liquid discharge section being formed atleast one of said supply-side member and said flow amount controlmember; each of said supply-side member and said flow amount controlmember being formed of a porous ceramic material including a ceramicsintered body which is formed with pores dispersedly located in saidsintered body and exposed to the sliding surfaces, said pores beingdefined respectively by surface layers forming part of said ceramicsintered body; and silicon contained in said ceramic sintered body, acontent of silicon being higher in at least a part of said surfacelayers than that in other part of said ceramic sintered body, whereinsaid surface layers have a structure and silicon in said surface layersforms part of said structure of said surface layers.
 2. A valve unit asclaimed in claim 1, wherein said at least one liquid supply sectionincludes a high temperature liquid supply section through which a hightemperature liquid is supplied, and a low temperature liquid supplysection through which a low temperature liquid is supplied, said lowtemperature liquid being lower in temperature than said high temperatureliquid, wherein said flow amount control member includes a sectiondefining a mixing chamber in which said high and low temperature liquidsare mixable with each other, said mixing chamber being communicable withsaid high and low temperature liquid supply sections and controllablerelative to said high and low temperature liquid supply sections inaccordance with a relative rotation of said flow amount control memberto said supply-side member.
 3. A method of producing a valve unit asclaimed in claim 1, comprising the following steps in the sequence setforth:preparing a porous ceramic material bymixing ceramic powder andhollow particles each of which contains silicon so as to obtain amixture; forming said mixture into a predetermined shape to obtain aformed body; and sintering said formed body at a temperature higher thana melting point of each hollow particle to obtain a sintered body formedwith pores and containing silicon, and using said porous ceramicmaterial to form said valve unit.
 4. A method as claimed in claim 3,wherein said hollow particles are selected from the group consisting ofSiO₂ --Al₂ O₃ system particles and SiO₂ system particles.
 5. A method asclaimed in claim 4, wherein said ceramic powder is at least one selectedfrom group consisting of Al₂ O₃ system powder, Si₃ N₄ system powder, SiCsystem powder, AlN system powder, and ZrO₂ system powder.
 6. A method asclaimed in claim 3, wherein each of said hollow particles is generallyspherical.
 7. A method as claimed in claim 3, wherein said ceramicpowder has an average particle size ranging from 1 to 20 μm, whereinsaid hollow particles has an average particle size ranging from 20 to250 μm.
 8. A valve unit comprising:a liquid supply-side member includingat least one liquid supply section through which liquid is supplied intosaid valve unit, and having a first sliding surface; a flow amountcontrol member having a second sliding surface which is in slidablecontact with said first sliding surface of said supply-side member, saidflow amount control member being relatively rotatable to said liquidsupply-side member so as to control an amount of said liquid to besupplied from said supply-side member; and a liquid discharge sectionthrough which said liquid controlled in the amount is discharged fromsaid valve unit, said liquid discharge section being formed at least oneof said supply-side member and said flow amount control member; each ofsaid supply-side member and said flow amount control member being formedof a porous ceramic material including a ceramic sintered body which isformed with pores dispersedly located in said sintered body and exposedto the sliding surfaces, said pores being defined respectively bysurface layers forming part of said ceramic sintered body, whereinparticles of said ceramic sintered body are comprised of at least onematerial selected from the group consisting of Al₂ O3 system powder, Si₃N₄ system powder, SiC system powder, AlN system powder and ZrO₂ systempowder, and wherein silicon is contained in said ceramic sintered body,a content of silicon being higher in at least a part of said surfacelayers than that in other parts of said ceramic sintered body, whereinsaid surface layers have a structure and silicon in said surface layersforms part of said structure of said surface layers, and wherein alubricant is present at least in pores exposed to the sliding surface.9. A valve unit comprising:a liquid supply-side member including atleast one liquid supply section through which liquid is supplied intosaid valve unit, and having a first sliding surface; a flow amountcontrol member having a second sliding surface which is in slidablecontact with said first sliding surface of said supply-side member, saidflow amount control member being relatively rotatable to said liquidsupply-side member so as to control an amount of said liquid to besupplied from said supply-side member; and a liquid discharge sectionthrough which said liquid controlled in the amount is discharged fromsaid valve unit, said liquid discharge section being formed at least oneof said supply-side member and said flow amount control member; each ofsaid supply-side member and said flow amount control member being formedof a porous ceramic material including a ceramic sintered body which isformed with pores dispersedly located in said sintered body and exposedto the sliding surfaces, said pores being defined respectively bysurface layers forming part of said ceramic sintered body; and siliconcontained in said ceramic sintered body, a content of silicon beinghigher in at least a part of said surface layers than that in otherparts of said ceramic sintered body, wherein said surface layers have astructure and silicon in said surface layers forms part of saidstructure of said surface layers, said porous ceramic material beingproduced by a method including the following steps in the sequence setforth; mixing ceramic powder and hollow particles which contain siliconso as to obtain a mixture; forming said mixture into a predeterminedshape to obtain a formed body; and sintering said formed body at atemperature higher than a melting point of each hollow particle toobtain said ceramic sintered body formed with pores and containingsilicon, the pores being defined respectively by the surface layerswhich are higher in silicon content than other parts of said ceramicsintered body.
 10. A valve unit as claimed in claim 1, wherein saidsurface layers are formed around each pore in said ceramic sinteredbody.